Sealant laminated composite, sealed semiconductor devices mounting substrate, sealed semiconductor devices forming wafer, semiconductor apparatus, and method for manufacturing semiconductor apparatus

ABSTRACT

Disclosed is a sealant laminated composite for collectively sealing a semiconductor devices mounting surface of a substrate on which semiconductor devices may be mounted or a semiconductor devices forming surface of a wafer on which semiconductor devices may be formed, including a support wafer that may be composed of silicon and an uncured resin layer that may be constituted of an uncured thermosetting resin formed on one side of the support wafer.

This is a Continuation of application Ser. No. 13/749,289 filed Jan. 24,2013, which claims the benefit of Japanese Patent Application No.2012-24452 filed on Feb. 7, 2012 and Japanese Patent Application No.2012-63158 filed Mar. 21, 2012. The disclosure of each of these priorapplications is hereby incorporated by reference herein in theirentireties.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to a sealant laminated composite capable ofcollective seal on a wafer level, a sealed semiconductor devicesmounting substrate, a sealed semiconductor devices forming wafer, asemiconductor apparatus, and a method for manufacturing a semiconductorapparatus.

2. Description of the Related Art

Various methods have been proposed and studied for sealing, on a waferlevel, a semiconductor devices mounting surface of a substrate on whichsemiconductor devices are mounted, or a semiconductor devices formingsurface of a wafer on which semiconductor devices are formed. A methodof sealing by spin coating, a method for sealing by screen printing(Patent Document 1), and a method where a composite sheet that isobtained by coating a hot-melt epoxy resin on a film support is used(Patent Documents 2 and 3) can be cited.

Recently, as the method for sealing, on a wafer level, the semiconductordevices mounting surface of a substrate on which semiconductor devicesare mounted among these methods, the following method is being put intopractical use as a mass-production method (Patent Document 4). Accordingto the method, after a film having an adhesive layer on both sidesthereof is stuck or an adhesive is coated by spin coating on an upperpart of a metal, a silicon wafer or a glass substrate, semiconductordevices are arranged, stuck and mounted on the substrate to form asemiconductor devices mounting surface. The semiconductor devicesmounting surface is then sealed by compression molding under a heatedcondition with a liquid epoxy resin or an epoxy molding compound.Similarly, as the method for sealing on a wafer level, the semiconductordevices forming surface of a wafer on which semiconductor devices areformed, a method where the semiconductor devices forming surface issealed with an liquid epoxy resin or an epoxy molding compound bycompression molding under a heated condition is being put into practicaluse recently as a mass production method.

According to the methods described above, when a wafer or a substrateconstituted of metal and so on, having a small diameter, for example,about 200 mm (8 inches) is used, even at the present time, there is noserious problem in sealing. However, when a semiconductor devicesmounting substrate or a semiconductor devices forming wafer, having alarge diameter of 300 mm (12 inches) or more, is sealed, there is aserious problem that, owing to contraction stress of a resin such as anepoxy resin during sealing and curing, the substrate or wafer is warped.Further, when the semiconductor devices mounting surface of asemiconductor devices mounting substrate having a large diameter issealed on a wafer level, a problem that owing to contraction stress of aresin such as an epoxy resin during sealing and curing, a semiconductordevice peels away from a substrate such as metal; thereforemass-production cannot be put into practical use.

As a method for solving the problems accompanying such a large diametersubstrate on which semiconductor devices are mounted or such a largediameter wafer on which semiconductor devices are formed, a method wherea filler is charged by about 90% by weight in a sealing resincomposition, and a method where the sealing resin composition is madelower in the elasticity to make smaller the contraction stress duringcuring can be cited (Patent Documents 1, 2, and 3).

However, when the filler is charged by about 90% by weight, theviscosity of a sealing resin composition rises, and when the sealingresin composition is molded by casting and sealed, a force is applied onsemiconductor devices mounted on a substrate. As a result, there occursa new problem in that the semiconductor devices peeled away from thesubstrate. Further, when the sealing resin is made low in theelasticity, warp of the sealed substrate on which semiconductor devicesare mounted or the sealed wafer on which semiconductor devices areformed is improved. However, a new problem in that sealing performancesuch as heat resistance and humidity resistance is deteriorated.Therefore, these solving methods were not fundamental solving methods.In view of the above situations, there is a demand for a sealingmaterial with which, even when a large diameter wafer or a largediameter substrate such as metal is sealed, without warp of thesubstrate or wafer and semiconductor devices peeled away from thesubstrate, the semiconductor devices mounting surface of a substrate onwhich semiconductor devices are mounted or the semiconductor devicesforming surface of a wafer on which semiconductor devices are formed canbe collectively sealed on a wafer level, and after sealing, sealingperformance such as the heat resistance and the humidity resistance isexcellent.

CITATION LIST Patent Literature

-   [Patent Document 1] Japanese Patent Application Publication No.    2002-179885-   [Patent Document 2] Japanese Patent Application Publication No.    2009-60146-   [Patent Document 3] Japanese Patent Application Publication No.    2007-001266-   [Patent Document 4] Published Japanese Translation of PCT    International Application No. 2004-504723

SUMMARY OF THE INVENTION

In addition to the above-mentioned, even when a sealing materialexcellent in the sealing performance such as the heat resistance and thehumidity resistance is used to seal, when an ionic impurity derived froma fiber base material or an ionic impurity intruded from the outside ofa semiconductor apparatus, and an ionic impurity derived from asemiconductor apparatus or a semiconductor devices mounting substrateare slightly contained in the sealing material, there is a problem inthat the reliability of the semiconductor apparatus is reduced.

The invention was performed to solve the above problems. It is an objectof the invention to provide a very versatile sealant laminated compositeby which, even when a thin substrate or wafer having a large diameter issealed, the substrate or the wafer can be prevented from warping and thesemiconductor devices can be suppressed from peeling, the semiconductordevices mounting surface of a substrate on which semiconductor devicesare mounted and the semiconductor devices forming surface of a wafer onwhich semiconductor devices are formed can be each collectively sealedon a wafer level, and after sealing, the sealing performance such as theheat resistance and the humidity resistance is excellent.

Further, it is an another object of the invention to provide a sealedsemiconductor devices mounting substrate and a sealed semiconductordevices forming wafer, sealed with the sealant laminated composite, asemiconductor apparatus obtained by dicing the sealed semiconductordevices mounting substrate and the sealed semiconductor devices formingwafer into each piece, and a method for manufacturing a semiconductorapparatus by using the sealant laminated composite.

In order to solve the above problems, the invention provides a sealantlaminated composite for collectively sealing a semiconductor devicesmounting surface of a substrate on which semiconductor devices aremounted or a semiconductor devices forming surface of a wafer on whichsemiconductor devices are formed, including a support wafer and anuncured resin layer constituted of an uncured thermosetting resin formedon one side of the support wafer.

With the sealant laminated composite, the support wafer can suppress thecontraction stress of the uncured resin layer during sealing and curing.Accordingly, even when a thin substrate or wafer having a large diameteris sealed, the warp of a substrate or a wafer and the peeling ofsemiconductor devices can be prevented from occurring, the semiconductordevices mounting substrate and semiconductor devices forming wafer canbe collectively sealed on a wafer level. After sealing, the sealantlaminated composite is excellent in the sealing performance such as theheat resistance and the humidity resistance and very versatile.

The difference between the expansion coefficient of the support waferand that of a substrate on which the semiconductor devices are mountedor a wafer on which the semiconductor devices are formed is preferableto be 3 ppm or less.

When the difference between the expansion coefficients is 3 ppm or less,the difference of the expansion coefficient of the support wafer andthat of the substrate or wafer on which the semiconductor devices aremounted or formed is reduced; thereby, the warp of the substrate orwafer to be sealed and the peeling of the semiconductor device can bepreferably, more surely suppressed.

Further, the thickness of the uncured resin layer depends on thethickness of semiconductor devices mounted or formed on a wafer. Inorder to secure high reliability, the thickness of a sealing resin layerfrom a top surface of the semiconductor devices (in a verticaldirection) is 10 to 2000 μm. From this, the thickness of the uncuredresin layer is preferable to be 20 μm or more and 2000 μm or less. Whenthe thickness of the uncured resin layer is 20 μm or more, a necessarythickness of the sealing resin layer on the semiconductor devices can besecured and thereby failure of filling properties due to extremethinness and non-uniformity of a film thickness can be preferablyprevented from occurring. When the thickness of the uncured resin layeris 2000 μm or less, it can be preferably prevented for the thicknessesof the sealed wafer and semiconductor apparatus from being too thick toenable high packaging density.

Further, the uncured resin layer preferably contains any one of an epoxyresin, a silicone resin, and an epoxy/silicone mixed resin that solidifyat less than 50° C. and melt at 50° C. or more and 150° C. or less.

The uncured resin layer is easy to handle and excellent in the sealingcharacteristics. With the uncured resin layer, the support wafer verysmall in the difference between the expansion coefficients can suppressthe contraction stress during curing of the uncured resin layercontaining these resins; accordingly, even when at large diameter, thinsubstrate or wafer is sealed, the substrate or wafer can be more surelyprevented from warping, semiconductor devices can be surely preventedfrom peeling, the sealant laminated composite that can collectively seala semiconductor devices forming surface of a wafer on whichsemiconductor devices are formed on a wafer level can be achieved. Thesealant laminated composite having the uncured resin layer containingthese resins is particularly excellent in the sealing characteristicssuch as the heat resistance and the humidity resistance after sealing.

Further, the support wafer is preferably a resin-impregnated fiber basematerial constituted of a fiber base material impregnated with athermosetting resin composition that is semi-cured or cured. The uncuredresin layer is preferably constituted of an uncured thermosetting resincomposition formed on one side of the resin-impregnated fiber basematerial with a thickness more than 200 μm and 2000 μm or less. At leastone of the thermosetting resin composition that is impregnated in thefiber base material and the thermosetting resin composition thatconstitutes the uncured resin layer preferably contains an ion trappingagent.

In the sealant laminated composite, the thickness of the uncured resinlayer is appropriate and the resin-impregnated fiber base materialhaving very small expansion coefficient can suppress the contractionstress of the uncured resin layer during sealing and curing.Accordingly, even when a large diameter organic substrate, a largediameter substrate such as metal, or wafer is sealed, while thesubstrate or wafer is prevented from warping and the semiconductordevices are prevented from peeling away from the substrate, thesemiconductor devices mounting surface can be collectively sealed on awafer level and, after sealing, the sealing characteristics such as theheat resistance and the humidity resistance are excellent. Further, bycontaining an ion trapping agent, a semiconductor apparatus high in thereliability can be provided, and a sealant laminated composite high inthe versatility is obtained.

Further, both the thermosetting resin composition that is impregnated inthe fiber base material and the thermosetting resin composition thatconstitutes the uncured resin layer are preferable to contain the iontrapping agent.

Thereby, ionic impurities intruding from the outside of thesemiconductor apparatus, and ionic impurities derived from the fiberbase material, the semiconductor devices, and the semiconductor devicemounting substrate can be surely trapped. Accordingly, the sealantlaminated composite can provide a semiconductor apparatus higher in thereliability.

Further, according to the invention, a sealed semiconductor devicesmounting substrate and a sealed semiconductor devices forming wafer areprovided. The sealed semiconductor devices mounting substrate and thesealed semiconductor devices forming wafer are obtained in such a mannerthat the semiconductor devices mounting surface of a substrate or thesemiconductor devices forming surface of a wafer on which semiconductordevices are mounted or formed is covered with the uncured resin layer ofthe sealant laminated composite, and the uncured resin layer is heatedand cured to collectively seal the semiconductor devices mounting orforming surface with the sealant laminated composite.

In the sealed semiconductor devices mounting substrate and the sealedsemiconductor devices forming wafer, the wafer can be prevented fromwarping and the semiconductor devices can be prevented from peeling.

Further, according to the invention, a semiconductor apparatus obtainedby dicing the sealed semiconductor devices mounting substrate or thesealed semiconductor devices forming wafer into each piece is provided.

The semiconductor apparatus is sealed with the sealant laminatedcomposite excellent in the sealing characteristics such as the heatresistance and the humidity resistance and manufactured by using asubstrate or wafer with suppressed warp; accordingly, the semiconductorapparatus has less residual stress and high quality.

Further, the invention provides a method for manufacturing asemiconductor apparatus, including the steps of: covering asemiconductor devices mounting surface of a substrate on whichsemiconductor devices are mounted or a semiconductor devices formingsurface of a wafer on which semiconductor devices are formed with theuncured resin layer of the sealant laminated composite; collectivelysealing the semiconductor devices mounting surface or the semiconductordevices forming surface by heating and curing the uncured resin layer toform a sealed semiconductor devices mounting substrate or a sealedsemiconductor devices forming wafer; and dicing the sealed semiconductordevices mounting substrate or the sealed semiconductor devices formingwafer into each piece to manufacture the semiconductor apparatus.

According to the method for manufacturing a semiconductor apparatus, inthe step of covering, the semiconductor devices mounting surface or thesemiconductor devices forming surface can be readily covered with theuncured resin layer of the sealant laminated composite without fillingfailure. Further, by using the sealant laminated composite, the supportwafer can suppress the contraction stress during curing of the uncuredresin layer; accordingly, in the step of sealing, the semiconductordevices mounting surface or the semiconductor devices forming surfacecan be collectively sealed, and, even when a large diameter, thinsubstrate or wafer is sealed, a sealed semiconductor devices mountingsubstrate and a sealed semiconductor devices forming wafer is preventedfrom warping and the semiconductor devices are prevented from peelingcan be obtained. Further, in the step of dicing into each piece, asemiconductor apparatus can be diced into each piece from the sealedsemiconductor devices mounting substrate and the sealed semiconductordevices forming wafer that are sealed with the sealant laminatedcomposite that is excellent in the sealing characteristics such as theheat resistance and the humidity resistance and suppressed from warping;accordingly, the method for manufacturing a semiconductor apparatus canmanufacture high quality semiconductor apparatus.

As described above, with the sealant laminated composite of theinvention, the support wafer can suppress the contraction stress of theuncured resin layer during curing and sealing; accordingly, even when alarge diameter, thin substrate or wafer is sealed, the substrate orwafer can be prevented from warping and the semiconductor devices can beprevented from peeling, the semiconductor devices forming surface of awafer on which semiconductor devices are formed can be collectivelysealed on a wafer level, and after sealing, a sealant laminatedcomposite is excellent in the sealing performance such as the heatresistance and the humidity resistance and very versatile. Further, Thesealed semiconductor devices mounting substrate and the sealedsemiconductor devices forming wafer that are sealed with the sealantlaminated composite are prevented from producing its warp and peeledsemiconductor devices. Further, a semiconductor apparatus obtained bydicing, into each piece, the sealed semiconductor devices mountingsubstrate and the sealed semiconductor devices forming wafer, which aresealed with the sealant laminated composite excellent in the sealingperformance such as the heat resistance and the humidity resistance andprevented from warping is high in quality. Further, according to themethod for manufacturing a semiconductor apparatus with sealantlaminated composite, a high quality semiconductor apparatus can bemanufactured.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an example of a cross-sectional view of a sealant laminatedcomposite of the invention;

FIG. 2 is an example of a cross-sectional view of (a) a sealedsemiconductor devices mounting substrate and (b) a sealed semiconductordevices forming wafer that are sealed with the sealant laminatedcomposite of the invention;

FIG. 3 is an example of a cross-sectional view of (a) a semiconductorapparatus of the invention manufactured from a sealed semiconductordevices mounting substrate, and (b) a semiconductor apparatus of theinvention manufactured from a sealed semiconductor devices formingwafer; and

FIG. 4 is an example of a flow-chart of a method for manufacturing asemiconductor apparatus from a substrate on which semiconductor devicesare mounted by using a sealant laminated composite of the invention.

DESCRIPTION OF THE PREFERRED EMBODIMENT

Hereinafter, a sealant laminated composite, a sealed semiconductordevices mounting substrate and a sealed semiconductor devices formingwafer, a semiconductor apparatus of the invention and a method formanufacturing a semiconductor apparatus will be described in detail.However, the invention is not limited thereto.

As described above, there is a demand for a sealant that can prevent thesubstrate or wafer from warping and the semiconductor device frompeeling, can collectively seal a semiconductor devices forming surfaceof a wafer on which semiconductor devices are formed on a wafer level,and is excellent in the sealing performance such as the heat resistanceor the humidity resistance after sealing and very versatile, even when alarge diameter, thin substrate or wafer on which semiconductor devicesare formed is sealed.

The inventors studied hard to solve the problems and found that with asealant laminated composite that has a support wafer and an uncuredresin layer constituted of an uncured thermosetting resin that islaminated and formed on one side of the support wafer, the contractionstress during resin curing can be suppressed by the support wafer, and,by reducing the difference of the expansion coefficient of the supportwafer and that of the wafer on which the semiconductor devices areformed, the contraction stress during curing of the uncured resin layercan be further suppressed. The inventors further found that, by thesuppression effect of the contraction stress, even when a largediameter, thin substrate or wafer is sealed, the substrate or wafer canbe prevented from warping and the semiconductor device can be preventedfrom peeling. The inventors also found that when the sealant laminatedcomposite of the invention is used, the semiconductor devices formingsurface of a semiconductor devices forming wafer can be collectivelysealed on a wafer level, and after the sealing, a sealant that isexcellent in the sealing performance such as the heat resistance and thehumidity resistance and very versatile can be obtained, thereby thesealant laminated composite of the invention was completed.

Further, the inventors found that the sealed semiconductor devicesmounting substrate and the sealed semiconductor devices forming waferthat are collectively sealed with the sealant laminated composite can beprevented from warping and producing peeled semiconductor devices, and,further, found that by dicing, into each piece, the sealed semiconductordevices mounting substrate and the sealed semiconductor devices formingwafer, in which its warp and the peel of the semiconductor device areprevented, a high quality semiconductor apparatus can be obtained;thereby, the sealed semiconductor devices mounting substrate and thesealed semiconductor devices forming wafer, and the semiconductorapparatus of the invention were completed.

Still further, the inventors found that the semiconductor devicesmounting surface or the semiconductor devices forming surface can bereadily covered with the sealant laminated composite, the semiconductordevices mounting surface or semiconductor devices forming surface can becollectively sealed by heating and curing an uncured resin layer of thesealant laminated composite, and when the sealed semiconductor devicesmounting substrate and the sealed semiconductor devices forming waferthat are sealed with the sealant laminated composite excellent in thesealing performance and suppressed from producing its warp and peelingof the semiconductor devices is diced into each piece, a high qualitysemiconductor apparatus can be manufactured, thereby the method formanufacturing a semiconductor apparatus of the invention was completed.

The sealant laminated composite of the invention is used to collectivelyseal the semiconductor devices mounting surface of a substrate on whichsemiconductor devices are mounted or the semiconductor devices formingsurface of a wafer on which semiconductor devices are formed, andincludes a support wafer and an uncured resin layer constituted of anuncured thermosetting resin formed on one side of the support wafer.

<Support Wafer>

The support wafer of the invention has no particular restriction on itsdiameter, thickness, and material, and can be selected in accordancewith a substrate or wafer on which semiconductor devices to be sealedare mounted or formed. Further, the difference between the expansioncoefficient of the support wafer and that of the substrate or wafer onwhich semiconductor devices are mounted or formed is preferably 3 ppm orless. More specifically, the difference between the linear expansioncoefficients at temperatures ranging from room temperature (25° C.±10°C.) to 200° C. is preferable to be 3 ppm/° C. or less (that is, 0 to 3ppm/° C.). When the difference between the expansion coefficients is setto 3 ppm or less, the contraction stress when an uncured resin layerdescribed below in more detail is cured can be sufficiently suppressedwith the support wafer. Accordingly, even when a large diameter, thinsubstrate or wafer is sealed with the sealant laminated composite of theinvention, the warp of the substrate or wafer and the peeling of thesemiconductor device can be more surely suppressed.

As the support wafer, a silicon (Si) wafer, a silicon carbide (SiC)wafer and the like can be used without particular limitation. However, asilicon wafer can be preferably used. In general, since a wafer on whichsemiconductor devices are mounted or formed is a silicon wafer, when asilicon wafer the same as that is used, the contraction stress when anuncured resin layer is cured can be further suppressed.

Further, in the invention, as the support wafer, a resin-impregnatedfiber base material obtained by impregnating a fiber base material witha thermosetting resin composition and the thermosetting resincomposition is then semi-cured or cured can be used. Such aresin-impregnated fiber base material has a very small expansioncoefficient and the contraction stress when an uncured resin layerdetailed below is cured can be suppressed; accordingly, even when alarge diameter organic resin substrate, a large diameter substrate suchas metal, or a large diameter wafer is sealed with the sealant laminatedcomposite of the invention, the substrate or wafer can be suppressedfrom warping and the semiconductor device can be suppressed frompeeling.

[Fiber Base Material]

As what can be used as the fiber base material, a glass fiber selectedfrom E-glass, S-glass, T-glass and D-glass is preferably used. Further,in general, when a glass fiber other than the above is used, owing toalkali ion components such as sodium contained much therein, thereliability as the sealant is reduced, and owing to the impuritiescontained much, the electric characteristics may be deteriorated.However, when, like in the invention, an ion trapping agent is containedin at least one of the thermosetting resin composition with which thefiber base material is impregnated and the thermosetting resincomposition that constitutes the uncured resin layer, also these fiberbase materials can be used. Thereby, even when a semiconductor apparatushaving a relatively thick sealing layer exceeding 200 μm is used, asemiconductor apparatus less in warp and high in the reliability can beobtained. Further, as required, other than the glass fiber, a highpurity quartz fiber can be used.

As conformations of the fiber base material, sheet-like ones such as aroving in which long fibrous filaments are pulled and aligned in onedirection, a fiber cloth and a nonwoven fabric, and a chop-strand matteare exemplified. However, as long as it can form a laminate, there is noparticular limitation.

[Thermosetting Resin Composition]

In the sealant laminated composite of the invention, at least one of thethermosetting resin composition with which the fiber base material isimpregnated and the thermosetting resin composition that constitutes theuncured resin layer contains an ion trapping agent. In particular, it isdesirable that both the thermosetting resin composition with which thefiber base material is impregnated and the thermosetting resincomposition that constitutes the uncured resin layer contain an iontrapping agent.

As the ion trapping agent, inorganic substances such as hydrotalcites,zinc molybdate, and rare earth oxides such as lanthanum oxide, and ionexchange resins can be used. As the ion trapping agent, an ion trappingagent that does not adversely affect on the reliability of asemiconductor apparatus is preferably selected without limiting tomaterials described above.

The above-described components work as an ion trapping agent andeffectively trap ionic impurities derived from the fiber base materialssuch as the glass fiber, ionic impurities intruding from the outside ofthe semiconductor apparatus, and ionic impurities derived from thesemiconductor devices and the semiconductor devices mounting organicsubstrate. Further, even when the sealing resin layer has a sealinglayer of relatively thick, in particular, a thickness more than 200 μm,the ion trapping agent is essential to reduce the warp of the substrateor to achieve high reliability of the semiconductor apparatus.

As the thermosetting resin composition, an epoxy resin, a siliconeresin, and an epoxy-silicone mixed resin, described below, that containhydrotalcites, zinc molybdate, or rare earth oxides such as lanthanumoxide as the ion trapping agent can be exemplified. However, athermosetting resin that is usually used to seal a semiconductor devicecan be used without particular limitation.

As a typical ion trapping agent, hydrotalcites represented by thefollowing formula will be described as an example. The hydrotalcites aredesirable to be 1 to 10 parts by mass with respect to 100 pats by massof a sum total of the thermosetting resin and a curing agent. When thehydrotalcites are contained by 1 parts by mass or more, a sufficientimpurity trapping capability can be obtained. When the hydrotalcites arecontained by 10 parts by mass or less, the impurity trapping capabilityis sufficient and the humidity resistance reflow property can besuppressed from deteriorating owing to an increase in moistureabsorption of the hydrotalcites themselves,

Mg_(x)Al_(y)(OH)_(2x+3y−2z)(CO₃)_(z) .mH₂O

wherein x, y and z each have relationships of 0<y/x≦1 and 0≦z/y<1.5, andm represents an integer.

Further, when zinc molybdate is used, zinc molybdate is desirablycontained by 0.5 parts by mass or more with respect to 100 parts by massof a sum total of the thermosetting resin and the curing agent. Whenzinc molybdate is contained by 0.5 parts by mass or more, sufficientimpurity trapping capability can be obtained. The upper limit of anaddition amount is not particularly limited. However, from the viewpointof maintaining the adhesiveness and workability, the addition amount isdesirable to be 5 to 50% by weight.

Still further, also rare earth oxide such as lanthanum oxide can be usedas an ion trapping agent. Among rare earth oxides, lanthanum oxide isdesirable.

A use amount of the lanthanum oxide is desirable to be 0.2 to 5 parts bymass with respect to 100 parts by mass of a sum total of thethermosetting resin and the curing agent. When the use amount is 0.2parts by mass or more, sufficient impurity trapping capability can beobtained. When the use amount is 5 parts by mass or less, the humidityresistance reflow property can be suppressed from deteriorating owing toan increase in the moisture absorption of lanthanum oxide itself.

The ion trapping agents may be used singularly or in a combination oftwo or more kinds thereof.

[Method for Fabricating Resin-Impregnated Fiber Base Material]

As a method for impregnating a fiber base material with a thermosettingresin composition, both a solvent method and a hot-melt method can beperformed. The solvent method is a method where a thermosetting resincomposition is dissolved in an organic solvent to fabricate a resinvarnish, and, after a fiber base material is impregnated with the resinvarnish, the solvent is heated to volatilize. The hot-melt method is amethod where a solid thermosetting resin composition is heated andmelted to impregnate the fiber base material therewith.

As a method for semi-curing a thermosetting resin composition that isimpregnated in the fiber base material, a method for semi-curing byheating the thermosetting resin composition that is impregnated in thefiber base material to desolvate is exemplified without particularlimitation. Further, as a method for curing the thermosetting resincomposition that is impregnated in the fiber base material, a method forcuring by heating the thermosetting resin composition that isimpregnated in the fiber base material can be exemplified withoutparticular limitation.

The thickness of the resin-impregnated fiber base material obtained byimpregnating the fiber base material with the thermosetting resincomposition and further by semi-curing or curing the thermosetting resincomposition is determined depending on a thickness of the fiber basematerial used such as fiber cloth. When a thick resin-impregnated fiberbase material is fabricated, the number of sheets of the fiber basematerial such as the fiber cloth is increased to laminate them.

In the invention, the semi-curing means a B-stage state (acuring-incomplete body of a thermosetting resin composition: a resin inthis state is softened when heated, and when brought into contact with acertain solvent, it swells but is not completely melted and dissolved),as defined in JIS K 6800 “Adhesive/Adhesion Terms”.

As a thickness of the resin-impregnated fiber base material, in both ofthe case where the thermosetting resin with which the fiber basematerial is impregnated is semi-cured and the case where the same iscured, a thickness of 50 μm to 1 mm is preferable and a thickness of 100μm to 500 μm is more preferable. A thickness of 50 μm or more ispreferable since it can suppress deformation caused when the thicknessis too small, and a thickness of 1 mm or less is preferable since it cansuppress the semiconductor apparatus itself from becoming too thick.

Moreover, the expansion coefficient of the resin-impregnated fiber basematerial in an X-Y direction at temperatures ranging from roomtemperature (25° C.±10° C.) to 200° C. is preferably 5 ppm/° C. or moreand 30 ppm/° C. or less, and more preferably 10 ppm/° C. or more and 25ppm/° C. or less.

When the expansion coefficient in an X-Y direction of theresin-impregnated fiber base material is 5 ppm/° C. or more and 30 ppm/°C. or less, the difference of expansion coefficient from that of thesubstrate on which semiconductor devices are mounted becomes smaller,the warp of the substrate to be sealed and the peeling of thesemiconductor devices from the substrate can be more surely suppressed.It is to be noted that the X-Y direction means a plane direction of theresin-impregnated fiber base material, and the expansion coefficient inan X-Y direction means an expansion coefficient measured by arbitrarilysetting an X axis and a Y axis in the plane direction of theresin-impregnated fiber base material.

The resin-impregnated fiber base material is important in order toreduce the warp after collective seal of the semiconductor devicesmounting surface and to reinforce the substrate having one or moresemiconductor devices aligned and bonded thereon. Therefore, a hard andrigid resin-impregnated fiber base material is desirable.

<Uncured Resin Layer>

The sealant laminated composite of the invention has an uncured resinlayer. The uncured resin layer is constituted of an uncuredthermosetting resin formed on one side of the support wafer. The uncuredresin layer serves as a resin layer for sealing.

Further, the thickness of the uncured resin layer depends on thethickness of semiconductor devices that are mounted or formed on thewafer. In order to secure high reliability, the thickness of the sealingresin layer from a top surface of the semiconductor devices (in avertical direction) is 10 to 2000 μm. From this, usually, the thicknessof the uncured resin layer is preferable to be 20 μm or more and 2000 μmor less. When the thickness of the uncured resin layer is 20 μm or more,preferably, a necessary thickness of the sealing resin layer can besecured on the semiconductor devices, and a failure of fillingproperties and an uneven film thickness owing to an extremely thinthickness can be suppressed from occurring. When the thickness is 2000μm or less, the thickness of the sealed wafer and semiconductorapparatus is prevented from being too thick to enable high packagingdensity.

Although the uncured resin layer is not limited in particular, anuncured resin layer constituted of a liquid epoxy resin or a solid epoxyresin, a silicone resin, or a mixed resin of the epoxy resin and thesilicone resin, which are generally used for sealing semiconductordevices, is preferable. In particular, it is preferable for the uncuredresin layer to contain any one of the epoxy resin, the silicone resin,and the epoxy-silicone mixed resin that are solidified at a temperatureless than 50° C. and molten at a temperature of 50° C. or higher and150° C. or less. With such an uncured resin layer, the layer can bereadily handled, manufactured and used as a sealing agent. Further,since the uncured resin layer is constituted of a thermosetting resin,the upper limit of the melting temperature of the uncured resin layer isdesirable to be equal to or less than a temperature at which itsreaction starts.

With such an uncured resin layer, a resin-impregnated fiber basematerial having a very small expansion coefficient can suppress thecontraction stress during curing of the uncured resin layer containingthese resins. Accordingly, even when a large diameter organic resinsubstrate, a large diameter substrate such as metal, or a wafer issealed, the warp of the substrate or wafer and the peeling of thesemiconductor devices from the substrate can be surely suppressed.Further, in particular, after sealing, a sealant laminated compositeexcellent in the sealing properties such as the heat resistance and thehumidity resistance can be obtained.

Further, the uncured resin layer is preferable to contain an iontrapping agent such as hydrotalcites, zinc molybdate, or lanthanumoxide, and any one of an epoxy resin, a silicone resin, and anepoxy-silicone mixed resin that are solidified at a temperature lessthan 50° C. and molten at a temperature that is 50° C. or higher. Theupper limit of the melting temperature depends on a reaction of thethermosetting resin composition and a catalyst used and is preferable tobe 180° C. or lower.

Epoxy Resin

The epoxy resin is not restricted in particular. Examples thereofinclude: a bisphenol type epoxy resin such as a bisphenol A epoxy resin,a bisphenol F epoxy resin, a 3,3′,5,5′-tetramethyl-4,4′-bisphenol typeepoxy resin, or a 4,4′-bisphenol type epoxy resin; epoxy resins obtainedby hydrogenating an aromatic ring of a phenol novolac-type epoxy resin,a cresol novolac-type epoxy resin, a bisphenol A novolac-type epoxyresin, a naphthalene diol-type epoxy resin, a tris phenylolmethane-typeepoxy resin, a tetrakis phenylolethane-type epoxy resin, and a phenoldicyclopentadiene novolac-type epoxy resin; and a known epoxy resin thatis liquid or solid at room temperature such as an alicyclic epoxy resin.Moreover, as required, a predetermined amount of other epoxy resin otherthan those described above can be also used together.

Since the uncured resin layer constituted of the epoxy resin serves asthe resin layer that seals the semiconductor devices, it is preferableto reduce halogen ions such as chlorine and alkali ions such as sodiumas much as possible. When a sample of 10 g is added to 50 ml ofion-exchange water, the solution is sealed and left to stand still in anoven at 120° C. for 20 hours, and ions are extracted at 120° C. underheating, any of extracted ions is desirable to be 10 ppm or less.

A curing agent for epoxy resins can be contained in the uncured resinlayer constituted of the epoxy resin. As the curing agent, it ispossible to use, for example, a phenol novolac resin, various kinds ofamine derivatives, an acid anhydride, or a curing agent obtained bypartially ring opening an acid anhydride or an acid anhydride group tothereby generate a carboxylic acid. Among these, the phenol novolacresin is desirably used to secure reliability of the semiconductorapparatus manufactured using the sealant laminated composite accordingto the invention. In particular, it is preferable to mix the epoxy resinand the phenol novolac resin such that a mixing ratio of epoxy groupsand phenolic hydroxyl groups is 1:0.8 to 1.3.

Additionally, to promote a reaction of the epoxy resin and the curingagent, as an reaction promoter, an imidazole derivative, a phosphinederivative, an amine derivative, or a metal compound such as an organicaluminum compound may be used, for example.

Various kinds of additives may be blended in the uncured resin layerconstituted of the epoxy resin as required. For example, for the purposeof improving properties of the resin, it is possible to add and blendadditives such as various kinds of thermoplastic resins, thermoplasticelastomers, organic synthetic rubbers, silicon-based low-stress agents,waxes, and halogen trapping agents.

[Silicone Resin]

As the silicone resin, a thermosetting silicone resin and others can beused. In particular, it is desirable for the uncured resin layerconstituted of the silicone resin to contain an addition-curablesilicone resin composition. As the addition-curable silicone resincomposition, a composition having (A) an organosilicon compound having anon-conjugated double bond, (B) organohydrogenpolysiloxane, and (C) aplatinum-based catalyst as essential components is particularlypreferable. The components (A) to (C) will be described hereinafter.

Component (A): Organosilicon Compound Having Non-conjugated Double Bond

As the (A) organosilicon compound having a non-conjugated double bond isexemplified by organopolysiloxane represented by a general formula (1),

R¹R²R³SiO—(R⁴R⁵SiO)_(a)—(R⁶R⁷SiO)_(b)—SiR¹R²R³,

wherein R¹ represents a non-conjugated double bond-containing univalenthydrocarbon group, R² to R⁷ each represent the same or differentunivalent hydrocarbon group, and a and b represent integers meeting0≦a≦500, 0≦b≦250, and 0≦a+b≦500.

In the general formula (1), R¹ is a non-conjugated doublebond-containing univalent hydrocarbon group, which is preferably anon-conjugated double bond-containing univalent hydrocarbon group havingan aliphatic unsaturated bond as typified preferably by a C₂ to C₈alkenyl group, particularly preferably by a C₂ to C₆ alkenyl group.

In the general formula (1), R² to R⁷ each are the same or differentunivalent hydrocarbon groups and exemplified preferably by a C₁ to C₂₀,particularly preferably C₁ to C₁₀ alkyl group, alkenyl group, arylgroup, or aralkyl group. Further, among these, R⁴ to R⁷ each are morepreferably a univalent hydrocarbon group excluding an aliphaticunsaturated bond, particularly preferably an alkyl group, an aryl group,or an aralkyl group that does not have an aliphatic unsaturated bondsuch as an alkenyl group. Furthermore, among these, R⁶ and R⁷ each arepreferably an aromatic univalent hydrocarbon group, more preferably, aC₆ to C₁₂ aryl group such as a phenyl group or a tolyl group.

In the general formula (1), a and b are integers meeting 0≦a≦500,0≦b≦250, and 0≦a+b≦500, and a preferably satisfies 10≦a≦500, bpreferably satisfies 0≦b≦150, and a+b preferably satisfies 10≦a+b≦500.

The organopolysiloxane represented by the general formula (1) can beobtained by an alkali equilibration reaction between a cyclicdiorganopolysiloxane such as a cyclic diphenylpolysiloxane or a cyclicmethylphenylpolysiloxane and a disiloxane such as adiphenyltetravinyldisiloxane or a divinyltetraphenyldisiloxane, whichconstitutes a terminal group. However, in this case, since a smallamount of a catalyst irreversibly advances polymerization in theequilibration reaction using an alkali catalyst (particularly strongalkali such as KOH), ring-opening polymerization alone quantitativelyproceeds, a terminal blocking ratio is high, and hence a silanol groupand a chloride component are not usually contained.

Organopolysiloxanes represented by the general formula (1) arespecifically exemplified by the following expression,

wherein k and m each represent an integer satisfying 0≦k≦500, 0≦m≦250,and 0≦k+m≦500, preferably 5≦k+m≦250, and 0≦m/(k+m)≦0.5.

As the component (A), other than organopolysiloxanes having astraight-chain structure represented by the general formula (1), asrequired, also organopolysiloxanes having a three-dimensional networkstructure including a trifunctional siloxane unit, a tetrafunctionalsiloxane unit, and the like can be used. The organosilicon compoundshaving a non-conjugated double bond (A) may be used singularly or in acombination of two or more kinds thereof.

It is preferable for an amount of a group (univalent hydrocarbon grouphaving a double bond bonded to a Si atom) having a non-conjugated doublebond in the organosilicon compound having a non-conjugated double bond(A) to be 1 to 50% by mol in all univalent hydrocarbon groups (allunivalent hydrocarbon groups bonded to Si atoms), more preferable to be2 to 40% by mol, particularly preferable to be 5 to 30% by mol. Anexcellent cured material can be obtained at the time of curing when anamount of the group having the non-conjugated double bond is 1% by molor more, and mechanical characteristics thereof are excellent at thetime of curing when the same is 50% by mol or less, which is preferable.

Furthermore, it is preferable for the organosilicon compound having anon-conjugated double bond (A) to have an aromatic univalent hydrocarbongroup (an aromatic univalent hydrocarbon group bonded to a Si atom), andit is preferable for the content of the aromatic univalent hydrocarbongroup to be 0 to 95% by mol in all univalent hydrocarbon groups (allunivalent hydrocarbon groups bonded to Si atoms), more preferable to be10 to 90% by mol, and particularly preferable to be 20 to 80% by mol.When an appropriate amount of the aromatic univalent hydrocarbon groupis contained in the resin, an advantage that mechanical characteristicsat the time of curing are excellent and manufacture can be wellperformed is obtained.

Component (B): Oranohydrogenpolysiloxane

As the component (B), organohydrogenpolysiloxanes having two or morehydrogen atoms bonded to silicon atoms (SiH groups) in one molecule arepreferable. The organohydrogenpolysiloxanes having two or more hydrogenatoms bonded to silicon atoms (SiH groups) in one molecule can serves asa cross-linker, and a cured material can be formed by an additionalreaction of the SiH group in the component (B) and the non-conjugateddouble bond-containing group such as a vinyl group or an alkenyl groupin the component (A).

Moreover, it is preferable for the organohydrogenpolysiloxane (B) tohave an aromatic univalent hydrocarbon group. With theorganohydrogenpolysiloxane (B) having the aromatic univalent hydrocarbongroup like this, compatibility with the component (A) can be enhanced.The organohydrogenpolysiloxanes (B) can be used singularly or in amixture of two or more kinds thereof, and organohydrogenpolysiloxane (B)having an aromatic hydrocarbon group, for example, can be contained as apart or all of the component (B).

Although not restricted, examples of the organohydrogenpolysiloxanes (B)include 1,1,3,3-tetramethyldisiloxane,1,3,5,7-tetramethylcyclotetrasiloxane,tris(dimethylhydrogensiloxy)methylsilane,tris(dimethylhydrogensiloxy)phenylsilane,1-glysidoxypropyl-1,3,5,7-tetramethylcyclotetrasiloxane,1,5-glysidoxypropyl-1,3,5,7-tetramethylcyclotetrasiloxane,1-glysidoxypropyl-5-trimethoxysilylethyl-1,3,5,7-tetramethylcyclotetrasiloxane,double-ended trimethylsiloxy group blocked methylhydrogenpolysiloxane, adouble-ended trimethylsiloxy group blockeddimethylsiloxane/methylhydrogensiloxane copolymer, double-endeddimethylhydrogensiloxy group blocked dimethylpolysiloxane, adouble-ended dimethylhydrogensiloxy group blockeddimethylsiloxane/methylhydrorgensiloxane copolymer, a double-endedtrimethylsiloxy group blocked methylhydrogensiloxane/diphenylsiloxanecopolymer, a double-ended trimethylsiloxy group blockedmethylhydrogensiloxane/diphenylsiloxane/dimethylsiloxane copolymer, atrimethoxysilane polymer, a copolymer constituted of (CH₃)₂HSiO_(1/2)units and SiO_(4/2) units, and a copolymer constituted of(CH₃)₂HSiO_(1/2) units, SiO_(4/2) units, and (C₆H₅) SiO_(3/2) units.

Further, also organohydrogenpolysiloxanes obtained by using unitsrepresented by the following structures can be used.

Further, as the organohydrogenpolysiloxanes (B), the following can begiven.

A molecular structure of the organohydrogensiloxanes (B) may be any oneof a straight chain structure, a cyclic structure, a branched chainstructure and a three-dimensional network structure. However, the numberof silicon atoms in one molecule (or the degree of polymerization in thecase of a polymer) is preferable to be two or more, more preferable tobe 2 to 1,000, and particularly preferable to be 2 to about 300.

A compounding amount of the organohydrogenpolysiloxane (B) is preferableto be an amount for hydrogen atoms bonded to silicon atoms (SiH group)in the component (B) per group having a non-conjugated double bond suchas an alkenyl group of the component (A) to be 0.7 to 3.0.

Component (C): Platinum-Based Catalyst

As the component (C), a platinum-based catalyst is used. As theplatinum-based catalyst (C), for example, chloroplatinic acid,alcohol-modified chloroplatinic acid, and a platinum complex having achelate structure can be cited. These can be used singularly or in acombination of two or more kinds thereof.

A compounding amount of the platinum-based catalyst (C) may be a curingeffective amount, that is, a so-called catalyst amount, and is usuallypreferable to be in the range of 0.1 to 500 ppm, in particular, 0.5 to100 ppm in terms of weight of platinum group metal per 100 parts by massof a total amount of the (A) component and (B) component.

The uncured resin layer constituted of the silicone resin becomes aresin layer for sealing semiconductor devices. Accordingly, it ispreferable for ions of halogen such as chlorine and ions of alkali suchas sodium are reduced as much as possible. Usually, it is desirable forany of ions to be 10 ppm or less when extracted at 120° C.

[Mixed Resin Constituted of Epoxy Resin and Silicone Resin]

As an epoxy resin and a silicone resin contained in the mixed resin, theepoxy resins and the silicone resins described above can be cited.

The uncured resin layer constituted of the mixed resin becomes a resinlayer for sealing semiconductor devices. Accordingly, it is preferablefor ions of halogen such as chlorine and ions of alkali such as sodiumare reduced as much as possible. Usually, it is desirable for any ofions to be 10 ppm or less when extracted at 120° C.

[Inorganic Filler]

In the uncured resin layer related to the invention, an inorganic fillercan be compounded. Examples of the inorganic fillers being compoundedinclude silicas such as fused silica and crystalline silica, alumina,silicon nitride, aluminum nitride, aluminosilicate, boron nitride, glassfiber and antimony trioxide. An average particle size and a shapethereof are not particularly limited.

As the inorganic filler to be added to the uncured resin layerconstituted of an epoxy resin in particular, in order to enhance thebonding strength between the epoxy resin and the inorganic filler, aninorganic filler that was treated in advance with a coupling agent suchas a silane coupling agent or a titanate coupling agent may be blended.

Examples of such the coupling agents include: epoxy functionalizedalkoxysilanes such as γ-glycidoxypropyltrimethoxysilane,γ-glycidoxypropylmethyldiethoxysilane, andβ-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; amino functionalizedalkoxysilane such as N-β(aminoethyl)-γ-aminopropyltrimethoxysilane,γ-aminopropyltriethoxysilane, andN-phenyl-γ-aminopropyltrimethoxysilane; and mercapto functionalizedalkoxysilane such as γ-mercaptopropyltrimethoxysilane. It is to be notedthat a compounding amount of the coupling agent used for a surfacetreatment and a surface treatment method are not restricted inparticular.

Also when adding to the uncured resin layer constituted of the siliconeresin composition, a material obtained by surface treating the inorganicfiller with the above-described coupling material may be blended.

A compounding amount of the inorganic filler is preferably 100 to 1300parts by mass and particularly preferably 200 to 1000 parts by mass withrespect to 100 parts by mass as a total weight of a resin in the epoxyresin composition or the silicone resin composition. When 100 parts bymass or more are added, sufficient strength can be obtained, and when1300 parts by mass or less are added, a reduction in flowability due tothickening and also a failure of filling properties due to a reductionin flowability can be suppressed, whereby the semiconductor devicesformed on the wafer and the semiconductor devices arranged and mountedon the substrate can be excellently sealed. It is preferable for theinorganic filler to be added in the range of 50 to 95% by weight orespecially 60 to 90% by weight in the entire composition constitutingthe uncured resin layer.

<Sealant Laminated Composite>

FIG. 1 shows an example of a cross-sectional view of a sealant laminatedcomposite according to the invention. The sealant laminated composite 10according to the invention has the support wafer 1, and the uncuredresin layer 2 constituted of an uncured thermosetting resin formed onone side of the support wafer.

[Method for Fabricating Sealant Laminated Composite]

When fabricating the sealant laminated composite according to theinvention, an uncured resin layer that is solid at 50° C. or less can beformed by coating a thermosetting resin such as a liquid epoxy resin ora silicone resin on one side of a support wafer by printing ordispensing under reduced pressure or vacuum and by heating.

Further, an uncured resin layer can be formed according to variousmethods that have been used in a conventional epoxy thermosetting resinor a conventional silicone thermosetting resin such as press molding orprinting an uncured thermosetting resin on one side of the supportwafer.

As another method for forming the uncured thermosetting resin layer onone side of the support wafer, a method where an epoxy thermosettingresin or a silicone thermosetting resin that is solid at roomtemperature is pressurized under heating, or a method where an epoxyresin composition that is liquefied by adding an appropriate amount of apolar solvent such as acetone is printed to form a thin film, and thesolvent is removed by heating under reduced pressure to uniformly forman uncured resin layer on one side of the support wafer can be used.

According to any of the methods, on one side of the support wafer, anuncured resin layer constituted of an uncured thermosetting resin thatis free of voids and volatile components and has a thickness of 20 to2000 μm or so can be formed.

[Substrate on which Semiconductor Devices are Mounted or Wafer on whichSemiconductor Devices are Formed]

The sealant laminated composite according to the invention is a sealantlaminated composite for collectively sealing the semiconductor devicesmounting surface of the substrate on which the semiconductor devices aremounted and the semiconductor devices forming surface of the wafer onwhich the semiconductor devices are formed. As the wafer used here, asilicon (Si) wafer and a SiC wafer are general, and, particularly, asilicone wafer is preferable. As an example of the substrate on whichthe semiconductor devices are mounted, the substrate 5 on which one ormore semiconductor devices 3 are mounted on through an adhesive 4 shownin FIG. 2A can be given, and as an example of the substrate, a BT(bismaleimidetriazine) resin organic substrate can be given. Further, asan example of the wafer on which the semiconductor devices are formed,the wafer 7 on which the semiconductor devices 6 are formed shown inFIG. 2B can be given. It is to be noted that examples of the substrateon which the semiconductor devices are mounted include a wafer on whichsemiconductor devices are mounted and aligned in multilayer.

<Sealed Semiconductor Devices Mounting Substrate and SealedSemiconductor Devices Forming Wafer>

FIGS. 2A and 2B show examples of cross-sectional views of the sealedsemiconductor devices mounting substrate and the sealed semiconductordevices forming wafer, which are sealed with the sealant laminatedcomposite according to the invention. In the sealed semiconductordevices mounting substrate 11 according to the invention, thesemiconductor devices mounting surface of the substrate 5 on which thesemiconductor devices 3 are mounted is covered with the uncured resinlayer 2 (see FIG. 1) of the sealant laminated composite 10, the uncuredresin layer 2 (see FIG. 1) is heated and cured to provide a cured resinlayer 2′ and the semiconductor devices mounting surface is collectivelysealed with the sealant laminated composite 10 (FIG. 2A). Furthermore,in the sealed semiconductor devices forming wafer 12 according to theinvention, the semiconductor devices forming surface of the wafer 7 onwhich the semiconductor devices 6 are formed is covered with the uncuredresin layer 2 (see FIG. 1) of the sealant laminated composite 10, theuncured resin layer 2 (see FIG. 1) is heated and cured to provide thecured resin layer 2′, and the semiconductor devices forming surface iscollectively sealed with the sealant laminated composite 10 (FIG. 2B).

The sealed semiconductor devices mounting substrate or the sealedsemiconductor devices forming wafer is prevented from warping and thesemiconductor devices mounting thereon are prevented from peeling.

<Semiconductor Apparatus>

FIGS. 3A and 3B show examples of a semiconductor apparatus according tothe invention. The semiconductor apparatus 13 according to the inventionis obtained by dicing the sealed semiconductor devices mountingsubstrate 11 (see FIG. 2) or the sealed semiconductor devices formingwafer 12 (see FIG. 2) into each piece. As described above, thesemiconductor apparatus 13 or 14 that is manufactured by dicing, intoeach piece, the sealed semiconductor devices mounting substrate 11 (seeFIG. 2) or the sealed semiconductor devices forming wafer 12 (see FIG.2) that is sealed with the sealant laminated composite having excellentsealing performance such as heat resistance or moisture resistance andsuppressed from producing its warp and semiconductor devices 3 peeledfrom the substrate can be a high-quality semiconductor apparatus. Whenthe sealed semiconductor devices mounting substrate 11 (see FIG. 2A) isdiced into each piece, the semiconductor apparatus 13 can be asemiconductor apparatus (FIG. 3A) that has the semiconductor devices 3mounted on the substrate 5 through the adhesive 4 and is sealed with thesealant laminated composite 10 including the cured resin layer 2′ andthe support wafer 1 from above (FIG. 3A). Furthermore, when the sealedsemiconductor devices forming wafer 12 (see FIG. 2B) is diced into eachpiece, the semiconductor apparatus 14 can be a semiconductor apparatusthat has the semiconductor devices 6 formed on the wafer 7 and is sealedwith the sealant laminated composite 10 including the cured resin layer2′ and the support wafer 1 from above (FIG. 3B).

<Method for Manufacturing Semiconductor Apparatus>

The method for manufacturing a semiconductor apparatus of the inventionincludes a covering step of covering the semiconductor devices mountingsurface of a substrate on which semiconductor devices are mounted or thesemiconductor devices forming surface of a wafer on which semiconductordevices are formed with the uncured resin layer of the sealant laminatedcomposite, a sealing step of collectively sealing the semiconductordevices mounting surface or the semiconductor devices forming surface byheating and curing the uncured resin layer to form a sealedsemiconductor devices mounting substrate or a sealed semiconductordevices forming wafer, and a step of dicing the sealed semiconductordevices mounting substrate or the sealed semiconductor devices formingwafer into each piece to manufacture the semiconductor apparatus.Hereinafter, the method for manufacturing a semiconductor apparatus ofthe invention will be described with reference to FIG. 4.

[Covering Step]

The covering step of the method for manufacturing a semiconductorapparatus of the invention is a step of covering the semiconductordevices mounting surface of the substrate 5 on which the semiconductordevices 3 are mounted through the adhesive 4, or the semiconductordevices forming surface of the wafer (not shown) on which thesemiconductor devices (not shown in the drawing) are formed with theuncured resin layer 2 of the sealant laminated composite 10 having thesupport wafer 1 and the uncured resin layer 2 (FIG. 4A).

[Sealing Step]

The sealing step of the a method for manufacturing a semiconductorapparatus of the invention is a step where to provide the cured resinlayer 2′, the semiconductor devices mounting surface of the substrate 5on which the semiconductor devices 3 are mounted or the semiconductordevices forming surface of the wafer (not shown in the drawing) on whichthe semiconductor devices (not shown in the drawing) are formed arecollectively sealed by heating and curing an uncured resin layer 2 ofthe sealant laminated composite 10, thereby a sealed semiconductordevices mounting substrate 11 or a sealed semiconductor devices formingwafer (not shown in the drawing) is provided (FIG. 4B).

[Dicing Step]

The dicing step of the method for manufacturing a semiconductorapparatus of the invention is a step of dicing the sealed semiconductordevices mounting substrate 11 or the sealed semiconductor devicesforming wafer (not shown in the drawing) into each piece to manufacturethe semiconductor apparatus 13 or 14 (see FIG. 3B) (FIG. 4C, 4D).

Hereinafter, more specific description will be given. At the coveringstep and the sealing step, when a vacuum lamination apparatus for use inlamination of a solder resist film or various kinds of insulator filmsis used, covering and sealing without void and warp can be carried out.As a method of lamination, it is possible to use any method of rolllamination, diaphragm type vacuum lamination, and air-pressurelamination. Among these, using both the vacuum lamination and theair-pressure lamination is preferable.

Other than the above, compression molding can be used for manufacture.Also in the molding according to the compression molding, when bymolding under reduced pressure conditions such as vacuum molding,failure such as voids and unfilling can be prevented from occurring.

Here, description will be given as to an example of using the vacuumlamination apparatus manufactured by Nichigo-Morton Co., Ltd. to seal asilicon wafer having a thickness of 200 μm, a diameter of 300 mm (12inches) and semiconductors formed thereon with the sealant laminatedcomposite having an uncured resin layer constituted of a uncuredthermosetting silicone resin having a thickness of 200 μm on one side ofa silicone wafer having a thickness of 150 μm and a diameter of 300 mm(12 inches).

Of plates that have upper and lower built-in heaters and are set to 150°C., the upper plate has a diaphragm rubber pressed against the heaterunder reduced pressure. A silicon wafer having a thickness of 200 μm anda diameter of 300 mm (12 inches) is set on the lower plate, and, thesealant laminated composite is set on one side of this silicon wafer sothat the uncured resin layer surface can fit to the semiconductordevices forming surface of the silicon wafer. Then, the lower plate ismoved up, the upper and lower plates are closely attached to each otherto form a vacuum chamber by an O-ring installed so as to surround thesilicon wafer set on the lower plate, and pressure in the vacuum chamberis reduced. When the pressure in the vacuum chamber is sufficientlyreduced, a valve of a pipe communicating with a vacuum pump from a spacebetween the diaphragm rubber of the upper plate and the heater is closedto send compressed air. As a result, the upper diaphragm rubber inflatesto sandwich the semiconductor forming silicon wafer and the sealantlaminated composite between the upper diaphragm rubber and the lowerplate, and vacuum lamination and curing of the thermosetting siliconeresin simultaneously advance, and sealing is completed. A curing time ofapproximately 3 to 20 minutes is enough. When the vacuum lamination isterminated, the pressure in the vacuum chamber is restored to a normalpressure, the lower plate is moved down, and the sealed silicon waferlaminate is taken out. The wafer without void or warp can be sealed bythe above-described process. The taken-out silicon wafer laminate isusually subjected to post cure at a temperature of 150 to 180° C. for 1to 4 hours, thereby electrical characteristics or mechanicalcharacteristics can be stabilized.

The covering and sealing steps using the vacuum lamination apparatus arenot restricted to the illustrated silicone resin, and they can be alsoused for the epoxy resin or a mixed resin of epoxy and silicone.

According to such a method for manufacturing a semiconductor apparatus,the semiconductor devices mounting surface or the semiconductor devicesforming surface can be easily covered with the uncured resin layer ofthe sealant laminated composite without a filling failure at thecovering step. Further, since the laminate is used, the support wafercan suppress the contraction stress of the uncured resin layer at thetime of curing, the semiconductor devices mounting surface or thesemiconductor devices forming surface can be thereby collectively sealedat the sealing step, and the sealed semiconductor devices mountingsubstrate or the sealed semiconductor devices forming wafer, in whichthe warp of the substrate or wafer and the peeling of the semiconductordevices from the substrate are suppressed, can be obtained even though alarge diameter, thin wafer or substrate is sealed. Furthermore, at thedicing step, a semiconductor apparatus can be obtained by dicing, intoeach piece, the sealed semiconductor devices mounting substrate or thesealed semiconductor devices forming wafer that is sealed with thesealant laminated composite that is excellent in the sealing performancesuch as heat resistance and humidity resistance and is suppressed inwarp; thus, the method for manufacturing a semiconductor apparatus canmanufacture a high quality semiconductor apparatus.

EXAMPLES

Hereinafter, with reference to a synthesis example of a silicone resinused as an uncured resin layer of a sealant laminated composite of theinvention and examples and comparative examples of a method formanufacturing a semiconductor apparatus that uses a sealant laminatedcomposite of the invention, the invention will be more detailed.However, the invention is not limited thereto.

Synthesis of Organosilicon Compound Having Non-Conjugated Double BondSynthesis Example 1 Organosilicon Compound Having Non-Conjugated DoubleBond (A1)

To synthesize an organosilicon compound having a non-conjugated doublebond (A1), 27 mol of organosilane represented as PhSiCl₃, 1 mol ofClMe₂SiO(Me₂SiO)₃₃SiMe₂Cl, and 3 mol of MeViSiCl₂ were dissolved in atoluene solvent, dropped into wafer, co-hydrolyzed, rinsed, neutralizedby alkali cleaning, and dehydrated, and then the solvent was stripped. Acomposition ratio of constituent units of this compound is representedby an expression:[PhSiO_(3/2)]_(0.27)[—SiMe2_(o)-(Me₂SiO)₃₃—SiMe₂O—]_(0.01)[MeViSiO_(2/2)]_(0.03).A weight-average molecular weight of this compound was 62,000, and amelting point thereof was 60° C. It is to be noted that Vi in thecomposition formula represents a vinyl group represented by (—CH═CH₂),and Me, Ph respectively represent a methyl group and a phenyl group(hereinafter, the same as the above).

Synthesis of Organohydrorgenpolysiloxane Synthesis Example 2Organohydrogenpolysiloxane (B1)

To synthesize an organohydrorgenpolysiloxane (B1), 27 mol oforganosilane represented as PhSiCl₃, 1 mol of ClMe₂SiO(Me₂SiO)₃₃SiMe₂Cl,and 3 mol of MeHSiCl₂ were dissolved in a toluene solvent, dropped intowafer, co-hydrolyzed, rinsed, neutralized by alkali cleaning, anddehydrated, and then the solvent was stripped. A composition ratio ofconstituent units of this resin is represented by an expression:[PhSiO_(3/2)]_(0.27)[—SiMe₂O-(Me₂SiO)₃₃—SiMe₂O—]_(0.01)[MeHSiO_(2/2)]_(0.03).A weight-average molecular weight of this compound was 58,000, and amelting point of the same was 58° C.

Example 1 Fabrication of Composition for Forming Uncured Resin LayerConstituted of Uncured Thermosetting Resin

With respect to a composition in which 50 parts by mass of theorganosilicon compound having a non-conjugated double bond (A1), 50parts by mass of organohydrogenpolysiloxane (B1), 0.2 parts by mass ofacetylene alcohol-based ethynylcyclohexanol as a reaction inhibitor, and0.1 parts by mass of an octyl alcohol-modified solution of achloroplatinic acid were added, 350 parts by mass of spherical silicahaving an average particle size of 5 μm were added at 60° C. and wellagitated by a planetary mixer heated to 60° C. to fabricate a siliconeresin composition (I-a). The composition was solid at room temperature(25° C.)

[Fabrication of Sealant Laminated Composite]

The silicone resin composition (I-a) was sandwiched between a siliconwafer (support wafer) having a diameter of 300 mm (12 inches) and afluororesin-coated PET film (release film) and compression molded for 5min under pressure of 5 ton at 80° C. using a heat press machine,thereby a sealant laminated composite (I-b) where an uncured resin layerconstituted of an uncured thermosetting resin having a thickness of 50μm is formed on one side of a silicon wafer (support wafer) wasfabricated.

[Covering and Sealing of Wafer on which Semiconductor Devices areFormed]

Then, a vacuum lamination apparatus (manufactured by Nichigo-Morton Co.,Ltd.) of which plate temperature was set to 130° C. was used to performcovering and sealing. First, a silicon wafer that has a diameter of 300mm (12 inches), a thickness of 125 μm and semiconductor devices formedthereon was set on a lower plate, covered with the silicone resincomposition (I-a) surface that is the uncured resin layer of the sealantlaminated composite (I-b) from which the release film was removed suchthat the composition surface fitted to a silicon wafer surface.Thereafter, the plate was closed and vacuum compression molding wasperformed for 5 min to cure and seal. After curing and sealing, asilicon wafer that was sealed with the sealant laminated composite (I-b)was further subjected to post cure at 150° C. for 2 hr, thereby a sealedsemiconductor devices forming wafer (I-c) was obtained.

Example 2 Substrate on which Semiconductor Devices are Mounted

On a 200 μm-thick silicon wafer having a diameter of 300 mm (12 inches),through an adhesive of which adhesion force deteriorates at a hightemperature, 400 pieces of silicon chips (shape: 5 mm×7 mm, thickness:125 μm) were arranged and mounted.

[Fabrication of Composition for Forming Uncured Resin Layer Constitutedof Uncured Thermosetting Resin]

After thoroughly mixing 60 parts by mass of cresol novolak type epoxyresin (trade name: EOCN 1020, manufactured by Nippon Kayaku Co., Ltd.),30 parts by mass of phenol novolak resin (trade name: H-4, manufacturedby Gun Ei Chemical Industry Co., Ltd.), 400 parts by mass of sphericalsilica (manufactured by Tatumori Ltd., average particle size: 7 μm), 0.2parts by mass of catalyst TPP (triphenylphosphine, manufactured by HokkoChemical Industry Co., Ltd.) and 0.5 parts by mass of a silane couplingagent (trade name: KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.)with a high-speed mixer, the mixture was heated and kneaded with acontinuous kneader to form it into a sheet, and then cooled. The sheetwas pulverized and thereby an epoxy resin composition (II-a) as agranular powder was obtained.

[Fabrication of Sealant Laminated Composite]

A silicon wafer (support wafer) having a diameter of 300 mm (12 inches)was set on a lower metal mold of a compression molding machine capableof heating and pressurizing under reduced pressure, and a granularpowder of the epoxy resin composition (II-a) was uniformly dispersed onthe wafer. The temperature of upper and lower metal molds was set to 80°C., a fluororesin-coated PET film (release film) was set on the uppermetal mold, the inside of the metal mold was depressurized to a vacuumlevel, and compression molding was performed for 3 min so that a resinthickness on the silicon wafer (support wafer) was 300 μm, thereby asealant laminated composite (II-b) was fabricated.

[Covering and Sealing of Substrate on which Semiconductor Devices areMounted]

Next, a vacuum lamination apparatus (manufactured by Nichigo-Morton Co.,Ltd.) of which a plate temperature was set to 170° C. was used toperform covering and sealing. First, a substrate on which semiconductordevices are mounted was set on a lower plate, and covered with the epoxyresin composition (II-a) surface that is an uncured resin layer of thesealant laminated composite (II-b) from which the release film wasremoved such that the composition surface fitted to the semiconductordevices mounting surface of the semiconductor devices mounting siliconwafer. The plate was then closed and vacuum compression molding wasperformed for 5 min to cure and seal. After curing and sealing, postcure was performed at 170° C. for 4 hours and a sealed semiconductordevices mounting substrate (II-c) was obtained.

Comparative Example 1 Fabrication of Sealing Sheet

A silicone resin composition (I-a) fabricated in the same manner as thatof Example 1 was sandwiched between a PET film (base film forpressurizing) and a fluororesin-coated PET film (release film),compression molded for 5 min under pressure of 5 ton at 80° C. using ahot press machine to mold into a film having a thickness of 50 μm,thereby a sealing sheet (III-b) constituted of only the silicone resincomposition (I-a) was fabricated. After molding, the sheet was cut intoa disc having a diameter of 300 mm (12 inches).

[Covering and Sealing of Wafer on which Semiconductor Devices areFormed]

Next, a vacuum lamination apparatus (manufactured by Nichigo-Morton Co.,Ltd.) of which a plate temperature was set to 130° C. was used toperform covering and sealing. First, a silicon wafer having a diameterof 300 mm (12 inches) and a thickness of 125 μm and semiconductordevices formed thereon was set on a lower plate, and stacked with thesealing sheet (III-b) constituted of only the silicone resin composition(I-a) from which the release film was removed. After peeling the PETfilm (base film for pressurizing), the plate was closed and vacuumcompression molding was performed for 5 min to cure and seal. Aftercuring and sealing, post cure was performed at 150° C. for 2 hours,thereby a sealed semiconductor devices forming wafer (III-c) wasobtained.

Comparative Example 2 Substrate on which Semiconductor Devices areMounted

On a 200 μm-thick silicon wafer having a diameter of 300 mm (12 inches),through an adhesive of which adhesion force deteriorates at a hightemperature, 400 of pieces of silicon chips (shape: 5 mm×7 mm,thickness: 125 μm) were arranged and mounted.

[Covering and Sealing of Substrate on which Semiconductor Devices areMounted]

A substrate on which the semiconductor devices are mounted was set on alower metal mold of a compression molding machine capable compressionmolding under reduced pressure, and a granular powder of the epoxy resincomposition (II-a) fabricated in the same manner as that of Example 2was uniformly dispersed. The temperature of upper and lower metal moldswas set to 170° C., a fluororesin-coated PET film (release film) was seton the upper metal mold and the inside of the metal mold wasdepressurized to a vacuum level, and compression molding was performedfor 3 min so that a resin thickness was 300 μm to cure and seal. Aftercuring and sealing, post cure was performed at 170° C. for 4 hours,thereby a sealed semiconductor devices mounting substrate (IV-c) wasobtained.

Warp, appearances, an adhesion state of the resin and the substrate,whether each semiconductor device has been peeled away from the wafer ornot were checked with respect to the semiconductor devices formingsubstrates (I-c) and (III-c), sealed in Example 1 and ComparativeExample 1, and the semiconductor devices mounting substrates (II-c) and(IV-c), sealed in Example 2 and Comparative Example 2. Table 1 showsresults. Here, in regard to the appearance, existence of voids and anunfilled state was checked, and the appearance was determined to beexcellent when the existence was not found. Moreover, as to the adhesionstate, the adhesion state was determined to be excellent when the resindid not peel away from the substrate at the time of molding.

TABLE 1 Comparative Comparative Example 1 Example 2 Example 1 Example 2Appearance Excellent Excellent Excellent Excellent Warp of wafer <0.1<0.1 12 10 (mm) Adhesion Excellent Excellent Excellent Excellent stateAppearance None None None Small void (void) Appearance None None NoneNone (unfilled state) Peel of — None — Yes semiconductor devices

Based on the above results, as shown by Comparative Examples 1 and 2using no support wafer according to the invention, it was found outthat, when the semiconductor devices forming surface of the wafer onwhich semiconductor devices are formed or the semiconductor devicesmounting surface of the substrate on which semiconductor devices weremounted were collectively sealed in these comparative examples, thesealed semiconductor devices forming wafer (III-c) and the sealedsemiconductor devices mounting substrate (IV-c) fabricated greatlywarped and the semiconductor devices peeled away from the substrate werefound (Table 1). On the other hand, as shown by the examples, in thesealed semiconductor devices forming wafer (I-c) and the sealedsemiconductor devices mounting substrate (II-c), sealed with the sealantlaminated composite according to the invention, it was found out thatthe warp of the substrate was greatly suppressed, the appearance and theadhesion state were excellent, and voids or unfilled states were notproduced either. Thus, the sealant laminated composite according to theinvention can suppress the contraction stress when curing the uncuredresin layer, whereby the warp of the substrate or the wafer and thepeeling of the semiconductor devices from the substrate can besuppressed.

Example 3 Fabrication of Resin-Impregnated Fiber Base Material SupportWafer

To obtain a base composition, 189 g of the organosilicon compound havinga non-conjugated double bond (A1) obtained in Synthesis Example 1, 189 gof the organohydrogenpolysiloxane (B1) obtained in Synthesis Example 2,0.2 g of acetylene alcohol-based ethynylcyclohexanol as a reactioninhibitor, 0.1 g of an octyl alcohol solution of 1% by mass ofchloroplatinic acid were added and the mixture was thoroughly stirredwith a planetary mixer heated at 60° C. To the base composition, addedwere 400 g of toluene as a solvent, 378 g of silica (trade name:ADMAFINE E5/24C, average particle size: about 3 μm, manufactured byAdmatechs Co., Ltd.) as an inorganic filler, 12 g of a hydrotalcitescompound (trade name: DHT-4A-2, Mg_(4.5)Al₂(OH)₁₃CO₃.3.5H₂O,manufactured by Kyowa Kasei Co., Ltd.), 40 g of zinc molybdate (tradename: 911B, manufactured by Sherwin-Williams Japan Co., Ltd.) and 2 g oflanthanum oxide (manufactured by Shin-Etsu Chemical Co., Ltd.), therebya toluene dispersion of a silicone resin composition was fabricated.

By dipping E glass cloth (manufactured by Nitto Boseki Co., Ltd.,thickness: 50 μm) as a fiber base material in the toluene dispersion ofthe silicone resin composition, the glass cloth was impregnated with thetoluene dispersion. The glass cloth was left to stand for 2 hours at 60°C. to volatilize toluene. On both sides of the E glass cloth from whichtoluene was volatilized, a film that is solid at room temperature (25°C.) was formed. The glass cloth was compression molded at 150° C. for 10min with a hot press machine to obtain a molded article, further, themolded article was subjected to second curing at 150° C. for 1 hour tocure an impregnated thermosetting resin composition, thereby a siliconeresin-impregnated fiber base material (V-a) was obtained.

Further, by dipping E glass cloth (manufactured by Nitto Boseki Co.,Ltd., thickness: 50 μm) as a fiber base material in the toluenedispersion of the silicone resin composition, the glass cloth wasimpregnated with the toluene dispersion, the glass cloth was left tostand for 2 hours at 60° C. to volatilize toluene, and, a siliconeresin-impregnated fiber base material (VI-a) where the impregnatedthermosetting resin composition was semi-cured was obtained. On bothsides of the E glass cloth from which toluene was volatilized, a filmthat is solid at room temperature (25° C.) was formed.

[Fabrication of Composition for Forming Uncured Resin Layer constitutedof Uncured Thermosetting Resin]

With respect to a composition where 50 parts by mass of theorganosilicon compound having a non-conjugated double bond (A1), 50parts by mass of organohydrogenpolysiloxane (B1), 0.2 parts by mass ofacetylene alcohol-based ethynylcyclohexanol as a reaction inhibitor, and0.1 parts by mass of an octyl alcohol-modified solution ofchloroplatinic acid were added, further, 350 parts by mass of sphericalsilica having an average particle size of 5 μm, 3 parts by mass of ahydrotalcites compound (trade name: DHT-4A-2,Mg_(4.5)Al₂(OH)₁₃CO₃.3.5H₂O, manufactured by Kyowa Kasei Co., Ltd.), 10parts by mass of zinc molybdate (trade name: 911B, manufactured bySherwin-Williams Japan Co., Ltd.) and 0.5 parts by mass of lanthanumoxide (manufactured by Shin-Etsu Chemical Co., Ltd.) were added and themixture was thoroughly stirred with a planetary mixer heated at 60° C.,thereby a silicone resin composition (V-b) was fabricated. Thecomposition was solid at room temperature (25° C.).

[Fabrication of Sealant Laminated Composite]

The silicone resin composition (V-b) was sandwiched between the siliconeresin-impregnated fiber base material (V-a) (expansion coefficient: x-ydirection 20 ppm) and a fluororesin-coated PET film (release film) andcompression molded at 80° C. under pressure of 5 ton for 5 min with ahot-press machine, thereby a sealant laminated composite (V-c) where anuncured resin layer constituted of an uncured thermosetting resincomposition having a thickness of 250 μm was formed on one side asilicone resin-impregnated fiber base material was fabricated. Afterthat, the sealant-laminated composite (V-c) was cut into a rectangle of60×220 mm.

[Covering and Sealing of Substrate on which Semiconductor Devices areMounted]

Next, a vacuum lamination apparatus (manufactured by Nichigo-Morton Co.,Ltd.) of which plate temperature was set to 130° C. was used to performcovering and sealing. First, an organic substrate made of a BT(bismaleimidotriazine) resin on which 14×14 mm Si chips (semiconductordevice, thickness: 150 μm) having a thickness of 125 μm were mounted wasset on a lower plate, and covered with the silicone resin composition(V-b) surface that was the uncured resin layer of the sealant laminatedcomposite (V-c) from which a release film was removed such that thecomposition surface fitted to the semiconductor device mounting surface.Thereafter, the plate was closed and vacuum compression molding wasperformed for 5 min to cure and seal. After curing and sealing, asubstrate that was sealed with the sealant laminated composite (V-c) wasfurther subjected to post cure at 150° C. for 2 hours, thereby a sealedsemiconductor devices mounting substrate (V-d) was obtained.

Example 4 Fabrication of Composition for Forming Uncured Resin Layerconstituted of Uncured Thermosetting Resin

With respect to a composition where 50 parts by mass of theorganosilicon compound having a non-conjugated double bond (A1), 50parts by mass of organohydrogenpolysiloxane (B1), 0.2 parts by mass ofacetylene alcohol-based ethynylcyclohexanol as a reaction inhibitor, and0.1 parts by mass of an octyl alcohol-modified solution ofchloroplatinic acid were added, further, 350 parts by mass of sphericalsilica having an average particle size of 5 μm, 3 parts by mass of ahydrotalcites compound (trade name: DHT-4A-2,Mg_(4.5)Al₂(OH)₁₃CO₃.3.5H₂O, manufactured by Kyowa Kasei Co., Ltd.), 10parts by mass of zinc molybdate (trade name: 911B, manufactured bySherwin-Williams Japan Co., Ltd.) and 0.5 parts by mass of lanthanumoxide (manufactured by Shin-Etsu Chemical Co., Ltd.) were added and themixture was thoroughly stirred with a planetary mixer heated at 60° C.,thereby a silicone resin composition (VI-b) was fabricated. Thecomposition was solid at room temperature (25° C.).

[Fabrication of Sealant Laminated Composite]

The silicone resin composition (VI-b) was sandwiched between thesilicone resin-impregnated fiber base material (VI-a) (expansioncoefficient: x-y direction 20 ppm) and a fluororesin-coated PET film(release film) and compression molded at 80° C. under pressure of 5 tonfor 5 min with a hot-press machine, thereby a sealant laminatedcomposite (VI-c) where an uncured resin layer constituted of an uncuredthermosetting resin composition having a thickness of 250 μm was formedon one side of a silicone resin-impregnated fiber base material (VI-a)was fabricated. After molding, the sealant laminated composite (VI-c)was cut into a rectangle of 60×220 mm.

[Covering and Sealing of Substrate on which Semiconductor Devices areMounted]

Next, a vacuum lamination apparatus (manufactured by Nichigo-Morton Co.,Ltd.) of which plate temperature was set to 130° C. was used to performcovering and sealing. First, a 14×14 mm square Si chip (semiconductordevice, thickness: 150 μm) was mounted on a lower plate, a BT substratehaving a thickness of 125 μm was set, and covered with the siliconeresin composition (VI-b) surface that was the uncured resin layer of thesealant laminated composite (VI-c) from which the release film wasremoved such that the composition surface fitted to the semiconductordevices mounting surface. The plate was then closed and vacuumcompression molding was performed for 5 min to cure and seal. Aftercuring and sealing, the substrate that was sealed with the sealantlaminated composite (VI-c) was further subjected to post cure at 150° C.for 2 hours, thereby a sealed semiconductor devices mounting substrate(VI-d) was obtained.

Example 5 Fabrication of Resin-Impregnated Fiber Base Material

A 70 μm-thick epoxy resin substrate in which E glass cloth was containedas a fiber base material and expansion coefficient (x, y axis) thereofwas controlled to 15 ppm by adding spherical silica having a particlesize of 0.3 μm was fabricated as a resin-impregnated fiber base material(VII-a).

[Fabrication of Composition for Forming Uncured Resin Layer constitutedof Uncured Thermosetting Resin]

After 60 parts by mass of cresol novolak type epoxy resin (trade name:EOCN 1020, manufactured by Nippon Kayaku Co., Ltd.), 30 parts by mass ofphenol novolak resin (trade name: H-4, manufactured by Gun Ei ChemicalIndustry Co., Ltd.), 400 parts by mass of spherical silica (manufacturedby Tatumori Ltd., average particle size: 7 μm), 3 parts by mass of ahydrotalcites compound (trade name: DHT-4A-2, Mg_(4.5)Al₂(OH)₁₃CO₃.3.5H₂O, manufactured by Kyowa Kasei Co., Ltd.), 10 parts bymass of zinc molybdate (trade name: 911B, manufactured bySherwin-Williams Japan Co., Ltd.), 0.5 parts by mass of lanthanum oxide(manufactured by Shin-Etsu Chemical Co., Ltd.), 0.2 parts by mass ofcatalyst TPP (triphenyl phosphine, manufactured by Hokko ChemicalIndustry Co., Ltd.) and 0.5 parts by mass of a silane coupling agent(trade name: KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.) werethoroughly mixed with a high-speed mixer, the mixture was heated andkneaded with a continuous kneader to form it into a sheet and thencooled. The sheet was pulverized, thereby an epoxy resin composition(VI-b) was obtained as a granular powder.

[Fabrication of Sealant Laminated Composite]

A resin-impregnated fiber base material (VIII-a) was set on a lowermetal mold of a compression molding machine capable of heating andpressurizing under reduced pressure, and a granular powder of the epoxyresin composition (VII-b) was uniformly dispersed on the material. Thetemperature of upper and lower metal molds was set to 80° C., afluororesin-coated PET film (release film) was set on the upper metalmold and the inside of the metal mold was depressurized to a vacuumlevel, and compression molding was performed for 3 minutes so that thethickness of the uncured resin layer may be 250 μm, thereby a sealantlaminated composite (VII-c) was fabricated. After molding, thesealant-laminated composite was cut into a rectangle of 60×220 mm.

[Covering and Sealing of Substrate on which Semiconductor Devices areMounted]

Next, a vacuum lamination apparatus (manufactured by Nichigo-Morton Co.,Ltd.) of which a plate temperature was set to 170° C. was used toperform covering and sealing. First, an epoxy resin substrate with a14×14 mm square Si chip (semiconductor device, thickness: 150 μm)mounted thereon and having a thickness of 125 μm was set on a lowerplate, and covered with the epoxy resin composition (VII-b) surface thatwas the uncured resin layer of the sealant laminated composite (VII-c)from which the release film was removed such that the compositionsurface fitted to the semiconductor devices mounting surface of theepoxy resin substrate. The plate was then closed and vacuum compressionmolding was performed for 5 min to cure and seal. After curing andsealing, post cure was performed at 170° C. for 4 hours, thereby asealed semiconductor devices mounting substrate (VII-d) was obtained.

Example 6 Substrate on which Semiconductor Devices are Mounted

On a 60×220 mm rectangular epoxy resin substrate, through an adhesive ofwhich adhesion force deteriorated at a high temperature, 20 pieces ofsilicon chips (shape: 14 mm×14 mm, thickness: 150 μm) were arranged andmounted.

[Covering and Sealing of Substrate on which Semiconductor Devices areMounted]

A vacuum lamination apparatus (manufactured by Nichigo-Morton Co., Ltd.)of which a plate temperature was set to 170° C. was used to cover andseal the substrate. First, the epoxy resin substrate on whichsemiconductor devices were mounted was set on a lower plate, a sealantlaminated composite (VIII-c) fabricated similarly to Example 3 exceptthat the thickness of the uncured resin layer was 210 μm was cut into a60×220 mm rectangle, and the resultant composite was set on thesubstrate. A peel film was removed, and an epoxy resin composition(VIII-b) surface that was a uncured resin layer of the sealant laminatedcomposite (VIII-c) was covered such that the composition surface fittedto the semiconductor devices mounting surface on the epoxy resinsubstrate. By closing a plate and by performing vacuum compressionmolding for 5 min, a resin on the silicon chip was then cured and sealedso that the thickness of the resin on the silicon chip was 60 μm (thethickness of a sealing resin layer is 210 μm). After curing and sealing,post cure was performed at 170° C. for 4 hours and a sealedsemiconductor devices mounting substrate (VIII-d) was obtained.

Example 7

With respect to a composition where 50 parts by mass of theorganosilicon compound having a non-conjugated double bond (A1), 50parts by mass of organohydrogenpolysiloxane (B1), 0.2 parts by mass ofacetylene alcohol-based ethynylcyclohexanol as a reaction inhibitor, and0.1 parts by mass of an octyl alcohol-modified solution ofchloroplatinic acid, 350 parts by mass of spherical silica having anaverage particle size of 5 μm were added and the mixture was thoroughlystirred with a planetary mixer heated at 60° C., thereby a siliconeresin composition (IX-b) was fabricated. The composition was solid at25° C.

[Fabrication of Sealant Laminated Composite]

The silicone resin composition (IX-b) was sandwiched between thesilicone resin-impregnated fiber base material (V-a) (expansioncoefficient: x-y direction 20 ppm) and a fluororesin-coated PET film(release film) and compression molded at 80° C. under pressure of 5 tonfor 5 min with a hot-press machine, thereby a sealant laminatedcomposite (IX-c) where an uncured resin layer constituted of a 2000μm-thick uncured thermosetting resin was formed on one side of thesilicone resin-impregnated fiber base material (V-a) was fabricated.After molding, the sealant laminated composite (IX-c) was cut into arectangle of 60×220 mm.

[Covering and Sealing of Substrate on which Semiconductor Devices areMounted]

Next, a vacuum lamination apparatus (manufactured by Nichigo-Morton Co.,Ltd.) of which a plate temperature was set to 130° C. was used toperform covering and sealing. First, a 14×14 mm square Si chip(semiconductor device, thickness: 725 μm) was mounted on a lower plate,a BT substrate having a thickness of 125 μm was set, and covered withthe silicone resin composition (IX-b) surface that was the uncured resinlayer of the sealant laminated composite (IX-c) from which the releasefilm was removed such that the composition surface fitted to thesemiconductor device mounting surface on the BT substrate. The plate wasthen closed and vacuum compression molding was performed for 5 min tocure and seal. After curing and sealing, the substrate that was sealedwith the sealant laminated composite (IX-c) was further subjected topost cure at 150° C. for 2 hours, thereby a sealed semiconductor devicesmounting substrate (IX-d) was obtained.

Comparative Example 3

With respect to a composition where 50 parts by mass of theorganosilicon compound having a non-conjugated double bond (A1), 50parts by mass of organohydrogenpolysiloxane (B1), 0.2 parts by mass ofacetylene alcohol-based ethynylcyclohexanol as a reaction inhibitor, and0.1 parts by mass of an octyl alcohol-modified solution ofchloroplatinic acid, 350 parts by mass of spherical silica having anaverage particle size of 5 μm were added and the mixture was thoroughlystirred with a planetary mixer heated at 60° C., thereby a siliconeresin composition (X-b) was fabricated. The composition was solid at 25°C.

[Fabrication of Sealing Sheet]

The silicone resin composition (X-b) was sandwiched between a PET film(base film for pressurizing) and a fluororesin-coated PET film (releasefilm), compression molded for 5 min under pressure of 5 ton at 80° C.using a hot press machine to mold into a film having a thickness of 250μm, thereby a sealing sheet (X-c) constituted of only a silicone resincomposition (X-b) was fabricated. After molding, the sheet was cut intoa 60×220 mm rectangle.

[Covering and Sealing of Substrate on which Semiconductor Devices areMounted]

Next, a vacuum lamination apparatus (manufactured by Nichigo-Morton Co.,Ltd.) of which a plate temperature was set to 130° C. was used toperform covering and sealing. First, to a lower plate, a 60×220 mm BTsubstrate having a thickness of 125 μm and 14×14 mm square Si chips(semiconductor device, thickness: 150 μm) mounted thereon was set, andstacked with the sealing sheet (X-c) constituted of only a siliconeresin composition (X-b) from which the release film was removed. Afterpeeling also a PET film (base film for pressurizing), the plate wasclosed and vacuum compression molding was performed for 5 min to cureand seal. After curing and sealing, post cure was performed at 150° C.for 2 hours, thereby a sealed semiconductor devices mounting substrate(X-d) was obtained.

Comparative Example 4 Substrate on which Semiconductor Devices areMounted

On a 60×220 mm BT resin substrate having a thickness of 300 μm, throughan adhesive of which adhesion force deteriorates at a high temperature,20 pieces of silicon chips (shape: 14 mm×14 mm, thickness: 150 μm) werearranged and mounted.

[Covering and Sealing of Substrate on which Semiconductor Devices areMounted]

The substrate on which semiconductor devices were mounted was set on alower metal mold of a compression molding machine capable compressionmolding under reduced pressure, and a granular powder of the epoxy resincomposition (XI-b) fabricated in the same manner as that of Example 3was uniformly dispersed on the substrate. The temperature of upper andlower metal molds was set to 170° C., a fluororesin-coated PET film(release film) was set on the upper metal mold and the inside of themetal mold was depressurized to a vacuum level, and curing and sealingwere performed by compression molding for 3 min so that the thickness ofthe uncured resin layer was 250 μm. After curing and sealing, post curewas performed at 170° C. for 4 hours, thereby a sealed semiconductordevices mounting substrate (XI-d) was obtained.

Warp, appearances, an adhesion state between the resin and thesubstrate, and whether each semiconductor device has been peeled awayfrom the metal substrate or not were checked with respect to the sealedsemiconductor devices mounting substrates that were sealed in Examples 3to 7, and Comparative Examples 3 to 4. Table 2 shows results. Here, inregard to the appearance, existence of voids and an unfilled state werechecked, and the appearance was determined to be excellent when theexistence was not found. Moreover, as to the adhesion state, theadhesion state was determined to be excellent when the resin did notpeel away from the substrate at the time of molding.

TABLE 2 Comparative Comparative Example 3 Example 4 Example 5 Example 6Example 7 Example 3 Example 4 (1) Added Added Not added Not added Added— — (2) Added Added Added Added Not added Not added Added (3) 250 250250 210 2000 250 250 (4) Excellent Excellent Excellent ExcellentExcellent Excellent Excellent (5)  0.2  0.3  0.1  0.3   0.3  12  9 (6)Excellent Excellent Excellent Excellent Excellent Excellent Excellent(7) Excellent Excellent Excellent Excellent Excellent Excellent Smallvoid (8) Not found Not found Not found Not found Not found Not found Notfound (9) E glass E glass E glass E glass E glass — — (10)  BT BT EpoxyEpoxy BT BT BT substrate substrate resin resin substrate substratesubstrate substrate substrate (11)  None None None None None Note: (1)An ion trapping agent in a thermosetting resin composition with which afiber base material is impregnated. (2) An ion trapping agent in athermosetting resin composition that constitutes an uncured resin layer.(3) The thickness of an uncured resin layer (μm) (4) Appearance (5) Warpof substrate (mm) (6) Adhesion state (7) Appearance (void) (8)Appearance (unfilling) (9) Glass fiber (10) Substrate (11) Peeling ofsemiconductor device from substrate

Based on the above results, as shown by Comparative Examples 3 and 4using no sealant-laminated composite according to the invention, it wasfound out that, when the semiconductor devices mounting surfaces werecollectively sealed in these comparative examples, the sealedsemiconductor devices mounting substrates to be fabricated greatlywarped and the semiconductor devices peeled away from the substrate werefound (Table 2). On the other hand, as shown by the examples, in thesealed semiconductor devices mounting substrates sealed with the sealantlaminated composite of the invention, it was found out that the warp ofthe substrate was greatly suppressed, the appearance and the adhesionstate were excellent, and voids or unfilled states were not producedeither. Thus, it was demonstrated that the resin-impregnated fiber basematerial according to the invention can suppress the contraction stresswhen curing the uncured resin layer, whereby the warp of the substrateand the peeling of the semiconductor devices from the substrate can besuppressed.

Further, the sealed semiconductor devices mounting substrates accordingto Examples 3 to 7 were diced into each piece, and 10 samples ofsemiconductor apparatuses each having a solder ball attached theretowere prepared for each of tests. The following heat resistance test andhumidity resistance test were performed on the semiconductorapparatuses. Since the sealed semiconductor devices mounting substratesformed according to Comparative Examples 3 and 4 was not able to bediced into each piece because they had large warp, the peeling of thesemiconductor devices from the substrate of the diced semiconductorapparatuses was not able to be evaluated.

[Heat Resistance Test]

The heat cycle test (repeating 1000 times a cycle of 10-minute hold at−25° C. and 10-minute hold at 125° C.) was performed to evaluate whetherthe continuity is maintained after test or not.

[Humidity Resistance Test]

Under condition of a temperature of 85° C. and relative humidity of 85%,a direct current voltage of 10 V was applied to both electrodes of acircuit, and by using a migration tester (trade name: MIG-86,manufactured by IMV Corporation), the number of short-circuit defectsafter 250 hours was measured.

TABLE 3 Example 3 Example 4 Example 5 Example 6 Example 7 Heat ExcellentExcellent Excellent Excellent Excellent resistance test (turning onelectricity after 1000 cycles) Humidity 0/10 0/10 0/10 0/10 0/10resistance test (the number of defects after 250 hr)

As shown in Table 3, in both of the heat resistance test and thehumidity resistance test, defects such as disconnection and crack werenot found in Examples 3 to 7. Based on this, it was demonstrated thatreliability of the semiconductor apparatus that was sealed with thesealant laminated composite of the invention is high.

The invention is not limited to the above-described embodiments. Theembodiments are only illustrations, and all that has substantially thesame configuration and the same effect with that of technical conceptsdescribed in claims of the invention is contained in the technical rangeof the invention.

What is claimed is:
 1. A sealant laminated composite for collectivelysealing a semiconductor devices mounting surface of a substrate on whichsemiconductor devices are mounted or a semiconductor devices formingsurface of a wafer on which semiconductor devices are formed,comprising: a support wafer composed of silicon; and an uncured resinlayer constituted of an uncured thermosetting resin formed on one sideof the support wafer.
 2. The sealant laminated composite according toclaim 1, wherein difference between an expansion coefficient of thesupport wafer and that of the substrate on which the semiconductordevices are mounted or the wafer on which the semiconductor devices areformed is 3 ppm or less.
 3. The sealant laminated composite according toclaim 1, wherein a thickness of the uncured resin layer is 20 μm or moreand 2000 μm or less.
 4. The sealant laminated composite according toclaim 2, wherein a thickness of the uncured resin layer is 20 μm or moreand 2000 μm or less.
 5. The sealant laminated composite according toclaim 1, wherein the uncured resin layer contains any one of an epoxyresin, a silicone resin, and an epoxy/silicone mixed resin that solidifyat less than 50° C. and melt at 50° C. or more and 150° C. or less. 6.The sealant laminated composite according to claim 2, wherein theuncured resin layer contains any one of an epoxy resin, a siliconeresin, and an epoxy/silicone mixed resin that solidify at less than 50°C. and melt at 50° C. or more and 150° C. or less.
 7. The sealantlaminated composite according to claim 3, wherein the uncured resinlayer contains any one of an epoxy resin, a silicone resin, and anepoxy/silicone mixed resin that solidify at less than 50° C. and melt at50° C. or more and 150° C. or less.
 8. The sealant laminated compositeaccording to claim 4, wherein the uncured resin layer contains anyone ofan epoxy resin, a silicone resin, and an epoxy/silicone mixed resin thatsolidify at less than 50° C. and melt at 50° C. or more and 150° C. orless.
 9. A sealed semiconductor devices mounting substrate, wherein asemiconductor devices mounting surface of a substrate on whichsemiconductor devices are mounted is covered with the uncured resinlayer of the sealant laminated composite according to claim 1, and theuncured resin layer is heated and cured to collectively seal thesemiconductor devices mounting surface with the sealant laminatedcomposite.
 10. A sealed semiconductor devices mounting substrate,wherein a semiconductor devices mounting surface of a substrate on whichsemiconductor devices are mounted is covered with the uncured resinlayer of the sealant laminated composite according to claim 8, and theuncured resin layer is heated and cured to collectively seal thesemiconductor devices mounting surface with the sealant laminatedcomposite.
 11. A sealed semiconductor devices forming wafer, wherein asemiconductor devices forming surface of a wafer on which semiconductordevices are formed is covered with the uncured resin layer of thesealant laminated composite according to claim 1, and the uncured resinlayer is heated and cured to collectively seal the semiconductor devicesforming surface with the sealant laminated composite.
 12. A sealedsemiconductor devices forming wafer, wherein a semiconductor devicesforming surface of a wafer on which semiconductor devices are formed iscovered with the uncured resin layer of the sealant laminated compositeaccording to claim 8, and the uncured resin layer is heated and cured tocollectively seal the semiconductor devices forming surface with thesealant laminated composite.
 13. A semiconductor apparatus obtained bydicing the sealed semiconductor devices mounting substrate according toclaim 9 into each piece.
 14. A semiconductor apparatus obtained bydicing the sealed semiconductor devices mounting substrate according toclaim 10 into each piece.
 15. A semiconductor apparatus obtained bydicing the sealed semiconductor devices forming wafer according to claim11 into each piece.
 16. A semiconductor apparatus obtained by dicing thesealed semiconductor devices forming wafer according to claim 12 intoeach piece.
 17. A method for manufacturing a semiconductor apparatus,comprising the steps of: covering a semiconductor devices mountingsurface of a substrate on which semiconductor devices are mounted, or asemiconductor devices forming surface of a wafer on which semiconductordevices are formed with the uncured resin layer of the sealant laminatedcomposite according to claim 1; collectively sealing the semiconductordevices mounting surface or the semiconductor devices forming surface byheating and curing the uncured resin layer to form a sealedsemiconductor devices mounting substrate or a sealed semiconductordevices forming wafer; and dicing the sealed semiconductor devicesmounting substrate or the sealed semiconductor devices forming waferinto each piece to manufacture the semiconductor apparatus.
 18. A methodfor manufacturing a semiconductor apparatus, comprising the steps of:covering a semiconductor devices mounting surface of a substrate onwhich semiconductor devices are mounted, or a semiconductor devicesforming surface of a wafer on which semiconductor devices are formedwith the uncured resin layer of the sealant laminated compositeaccording to claim 8; collectively sealing the semiconductor devicesmounting surface or the semiconductor devices forming surface by heatingand curing the uncured resin layer to form a sealed semiconductordevices mounting substrate or a sealed semiconductor devices formingwafer; and dicing the sealed semiconductor devices mounting substrate orthe sealed semiconductor devices forming wafer into each piece tomanufacture the semiconductor apparatus.